JP4866370B2 - Use of thermoplastic compositions in the thermal protection of substrates - Google Patents
Use of thermoplastic compositions in the thermal protection of substrates Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
- C08G81/024—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G
- C08G81/028—Block or graft polymers containing sequences of polymers of C08C or C08F and of polymers of C08G containing polyamide sequences
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
- B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (co)polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/04—Coating
- C08J7/0427—Coating with only one layer of a composition containing a polymer binder
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/02—2 layers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/304—Insulating
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2597/00—Tubular articles, e.g. hoses, pipes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/31504—Composite [nonstructural laminate]
- Y10T428/31725—Of polyamide
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- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Laminated Bodies (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
- Other Resins Obtained By Reactions Not Involving Carbon-To-Carbon Unsaturated Bonds (AREA)
Description
本発明は、種々の基材の熱的保護または高温での熱的安定性を有する製品または部品の製造での、ポリアミドブロックがグラフトされた官能性エチレンコポリマーを主成分とするナノ構造の熱可塑性組成物の使用に関するものである。 The invention relates to the thermoplasticity of nanostructures based on functional ethylene copolymers grafted with polyamide blocks in the manufacture of products or parts with thermal protection of various substrates or thermal stability at high temperatures. It relates to the use of the composition.
下記文献に記載のポリオレフィン幹ポリマーにポリアミドブロックがグラフトされたコポリマーは共連続ナノ構造を有するアロイ(alliage co-continu nanostructure)を形成している。
上記のポリオレフィンはエチレン/無水マレイン酸およびエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマーの中から選択され、このコポリマーは優れた熱機械特性を有している。この性質はこのグラフトコポリマーを可撓性エチレンポリマー等の可撓性ポリオレフィン中に再分散した場合でも保持される。このアロイは接着剤、フィルム、防水布、カレンダー製品、電気ケーブル、成形粉末(例えばスラッシュ成形用)等の用途がある。 The above polyolefins are selected from among ethylene / maleic anhydride and ethylene / alkyl (meth) acrylate / maleic anhydride copolymers, which copolymers have excellent thermomechanical properties. This property is retained even when the graft copolymer is redispersed in a flexible polyolefin such as a flexible ethylene polymer. This alloy has uses such as an adhesive, a film, a waterproof cloth, a calendar product, an electric cable, and a molding powder (for example, for slush molding).
現在、熱的安定性および耐熱挙動を向上させるのに用いられている熱可塑性材料はポリプロピレン(PP)マトリクス中にエチレン−プロピレン−ジエンモノマー(EPDM)コポリマーを分散させたポリマーである熱可塑性エラストマー(例えばエクソン社のサントプレン、SANTOPRENE、登録商標)、塩素化ポリマー(アルケマ社のサンプレン、SUNPRENE、登録商標)、加硫されたスーパー熱可塑性(Super-TPV)、例えばデュポン社のETPV型およびダウ(Dow Corning Mulibase)社のTPSiV型等である。 The thermoplastic material currently used to improve thermal stability and heat resistant behavior is a thermoplastic elastomer (polymer with ethylene-propylene-diene monomer (EPDM) copolymer dispersed in a polypropylene (PP) matrix. Exxon's Santoprene, SANTOPRENE®, chlorinated polymers (Arkema's Sanprene, SUNPRENE®), vulcanized super-thermoplastic (Super-TPV), eg DuPont's ETPV type and Dow Corning Mulibase) TPSIV type.
本発明者は、150℃以上、さらには200℃以上でも優れた熱的安定性および耐熱挙動を示す製品が得られる、ポリオレフィンの可撓性とポリアミドの熱的挙動とを合わせ持ち、安定剤のタイプおよびレベルを有する組成物(ポリオレフィン/ポリアミド)の領域を定義することに成功した。機械特性は上記温度以下ではエージング後でもほとんど変らない。 The present inventor combines the flexibility of polyolefin and the thermal behavior of polyamide to obtain a product exhibiting excellent thermal stability and heat resistance even at 150 ° C. or higher, or even 200 ° C. or higher. We have successfully defined the domain of compositions (polyolefin / polyamide) having types and levels. The mechanical properties hardly change even after aging below the above temperature.
本発明の対象は、エチレン/無水マレイン酸およびエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマーの中から選択されるポリオレフィン幹ポリマーと、少なくとも一種のポリアミドグラフト鎖とから成る、ポリアミドブロックを有するグラフトコポリマーを主成分とするナノ構造型の熱可塑性組成物の、150℃以上の温度での基材の熱保護での使用において、上記組成物の少なくとも一つの層が基材上に形成(depose)されていることを特徴とする使用にある。 The subject of the present invention is a graft having a polyamide block consisting of a polyolefin backbone polymer selected from among ethylene / maleic anhydride and ethylene / alkyl (meth) acrylate / maleic anhydride copolymers and at least one polyamide graft chain. In the use of a copolymer-based nanostructured thermoplastic composition in the thermal protection of a substrate at temperatures above 150 ° C., at least one layer of the composition is deposited on the substrate It is in use characterized by being.
本発明のポリオレフィン幹ポリマーはエチレン/アルキル(メタ)アクリレート/無水マレイン酸ターポリマーである。
本発明のグラフト鎖はカプロラクタム、11−アミノウンデカン酸またはドデカラクタムの残基から形成されるホモポリマーか、これら3種のモノマーの少なくとも2種の中から選択される残基から成るコポリアミドである。
ポリアミドグラフト鎖はモノ−NH2−末端を有するPA−6ポリアミドまたはモノ−NH2−末端を有するPA−6/11コポリアミドで、分子量は1000〜5000g/molであるのが好ましい。
本発明の熱可塑性組成物を形成して得られる被覆層は剛体の支持体または支持体または軟質または可撓性の基材の両方を熱的に保護する層に適している。
The polyolefin backbone polymer of the present invention is an ethylene / alkyl (meth) acrylate / maleic anhydride terpolymer.
The graft chain of the present invention is a homopolymer formed from the residues of caprolactam, 11-aminoundecanoic acid or dodecalactam, or a copolyamide consisting of residues selected from at least two of these three monomers. .
Polyamide graft chains mono -NH 2 - PA-6 polyamide or mono -NH 2 having terminal - with PA-6/11 copolyamide having terminal, molecular weight is preferably 1000~5000g / mol.
The coating layer obtained by forming the thermoplastic composition of the present invention is suitable for a rigid support or a layer that thermally protects both a support or a soft or flexible substrate.
「支持体または基材」という用語は任意タイプの合成ポリマー材料(熱可塑性または熱硬化性)、鉱物または植物由来の天然材料および金属材料で作られたものを意味する。
本発明は特に、ポリアミド、特にPA−11またはPA−12タイプの可撓性ポリアミドで作られた基材の被覆での本発明の熱可塑性組成物の使用に関するものである。
The term “support or substrate” means made of any type of synthetic polymeric material (thermoplastic or thermosetting), mineral or plant-derived natural and metallic materials.
The invention particularly relates to the use of the thermoplastic composition of the invention in the coating of substrates made of polyamides, in particular flexible polyamides of the PA-11 or PA-12 type.
本発明では被覆層を共押出で基材層上に形成する(特にパイプまたはチューブを製造する場合)。特に、このチューブまたはパイプは、PA−11および/またはPA−12タイプのポリアミドの内層と本発明の熱可塑性組成物から成る外層とを含む流体の輸送ライン、特にガソリン輸送用の2層チューブに好ましく適用される。
しかし、本発明は単層の被覆の製造に限定されるものではなく、多層の被覆、特に複合構造物の製造も含むものである。
In this invention, a coating layer is formed on a base material layer by coextrusion (especially when manufacturing a pipe or a tube). In particular, the tube or pipe is used in a fluid transport line, in particular a two-layer tube for gasoline transport, comprising an inner layer of polyamide of PA-11 and / or PA-12 type and an outer layer made of the thermoplastic composition of the invention. Preferably applied.
However, the invention is not limited to the production of single layer coatings, but also includes the production of multilayer coatings, especially composite structures.
本発明の別の対象は、200℃以上の温度で熱的安定性を有する製品または部品の製造での、エチレン/無水マレイン酸およびエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマーの中から選択されるポリオレフィン幹ポリマーと少なくとも一種のポリアミドグラフト鎖とから成るポリアミドブロックを有するグラフトコポリマーを主成分とするナノ構造タイプの熱可塑性組成物の使用にある。
この利用分野としては特に、自動車製造時にエンジンフード下で使用される固定ジョンイトおよび部品が挙げられる。
Another subject of the invention is selected from among ethylene / maleic anhydride and ethylene / alkyl (meth) acrylate / maleic anhydride copolymers in the manufacture of products or parts having thermal stability at temperatures above 200 ° C. The use of a nanostructured thermoplastic composition based on a graft copolymer having a polyamide block comprising a polyolefin backbone polymer and at least one polyamide graft chain.
This field of use includes in particular fixed joints and parts used under engine hoods during automobile manufacture.
従来技術に対する本発明の特性および利点は下記の通り:
(1)本発明のアロイ構造は独特である(ナノ構造による安定化した共連続構造がポリオレフィンの可撓性とポリアミドの耐熱挙動とを組合せたものに与えられる)。
(2)熱的安定性、耐加水分解安定性、熱可塑性成形加工性が同時に得られる。
(3)層間の結合層無しに、二層構造を共押出で一段階で作ることができる。
The characteristics and advantages of the present invention over the prior art are as follows:
(1) The alloy structure of the present invention is unique (a stabilized co-continuous structure with nanostructures is given to a combination of the flexibility of polyolefin and the heat resistant behavior of polyamide).
(2) Thermal stability, hydrolysis resistance, and thermoplastic moldability can be obtained at the same time.
(3) A two-layer structure can be made in one step by coextrusion without an interlayer tie layer.
従って、利点をまとめると以下のようになる:
(1) 熱可塑性エラストマー(TPE)および塩素化ポリマー(PVC)に対する利点:
(1) Advantages over thermoplastic elastomers (TPE) and chlorinated polymers (PVC):
(2) 「超」熱可塑性加硫物に対する利点:
二層チューブにおける本発明被覆の利点としては、(本発明被覆層を用いることで)被覆チューブの伸びと衝撃特性がチューブ単独の場合より良くなることが挙げられる、すなわち:
(1)PAチューブがガソリンと接触しなかったので伸びは300%を超える。
(2)衝撃強度:本発明の熱可塑性組成物は延性−脆性遷移が極めて低く(シャルピーノッチ付き衝撃で<−50℃)、衝撃強度が優れている。
Advantages of the coating of the present invention in a two-layer tube include (by using the coating layer of the present invention) that the elongation and impact properties of the coated tube are better than with the tube alone:
(1) Since the PA tube did not come into contact with gasoline, the elongation exceeds 300%.
(2) Impact strength: The thermoplastic composition of the present invention has a very low ductile-brittle transition (<-50 ° C. with Charpy notch impact) and excellent impact strength.
以下、本発明の対象である使用で使用される熱可塑性組成物の主成分について詳細に説明する。
ポリアミドブロックを有するグラフトコポリマーはアミン末端を有するポリアミドをポリオレフィン幹ポリマーにグラフトまたは共重合によって固定された不飽和モノマー(X)の残基と反応させて得られる。
Hereinafter, the main components of the thermoplastic composition used in the use which is the subject of the present invention will be described in detail.
The graft copolymer having a polyamide block is obtained by reacting an amine-terminated polyamide with a residue of an unsaturated monomer (X) fixed to a polyolefin backbone polymer by grafting or copolymerization.
上記不飽和モノマー(X)は例えば不飽和エポキシドまたは不飽和カルボン酸無水物にすることができ、この不飽和カルボン酸無水物の例としては無水マレイン酸、無水イタコン酸、無水シトラコン酸、無水アリルコハク酸、1,2−シクロヘキシ−4−エンジカルボン酸無水物、4-メチレン−1,2−シクロヘキシ−4−エンジカルボン酸無水物、ビシクロ[2,2,1]ヘプト−5−エン−2,3−ジカルボン酸無水物およびX-メチルビシクロ[2,2,1]ヘプト−5−エン−2,2−ジカルボン酸無水物が挙げられる。無水マレイン酸を用いるのが好ましい。無水物の全部または一部を不飽和カルボン酸、例えば(メタ)アクリル酸に代えても本発明の範囲を逸脱するものではない。不飽和エポキシドの例は既に述べた通りのものである。 The unsaturated monomer (X) can be, for example, an unsaturated epoxide or an unsaturated carboxylic acid anhydride. Examples of the unsaturated carboxylic acid anhydride include maleic anhydride, itaconic anhydride, citraconic anhydride, and allyl succinic anhydride. Acid, 1,2-cyclohexyl-4-enedicarboxylic anhydride, 4-methylene-1,2-cyclohexyl-4-enedicarboxylic anhydride, bicyclo [2,2,1] hept-5-ene-2, Examples include 3-dicarboxylic acid anhydride and X-methylbicyclo [2,2,1] hept-5-ene-2,2-dicarboxylic acid anhydride. It is preferred to use maleic anhydride. Replacing all or part of the anhydride with an unsaturated carboxylic acid such as (meth) acrylic acid does not depart from the scope of the present invention. Examples of unsaturated epoxides are those already mentioned.
ポリオレフィン幹ポリマーのポリオレフィンはα−オレフィンまたはジオレフィン、例えばエチレン、プロピレン、1−ブテン、1−オクテンまたはブタジエンのホモポリマーまたはコポリマーである。例としては下記を挙げることができる:
(1)ポリエチレンのホモポリマーおよびコポリマー、特にLDPE、HDPE、LLDPE(直鎖低密度ポリエチレン)、VLDPE(超低密度ポリエチレン)およびメタロセンポリエチレン、
(2)プロピレンのホモポリマーまたはコポリマー、
(3)エチレン/αオレフィンコポリマー、例えばエチレン/プロピレンコポリマー、EPR(エチレン/プロピレンゴム)およびエチレン/プロピレン/ジエンモノマー(EPDM)コポリマー、
The polyolefin of the polyolefin backbone polymer is a homopolymer or copolymer of an α-olefin or diolefin such as ethylene, propylene, 1-butene, 1-octene or butadiene. Examples include the following:
(1) Polyethylene homopolymers and copolymers, in particular LDPE, HDPE, LLDPE (linear low density polyethylene), VLDPE (very low density polyethylene) and metallocene polyethylene,
(2) propylene homopolymer or copolymer,
(3) ethylene / alpha olefin copolymers, such as ethylene / propylene copolymers, EPR (ethylene / propylene rubber) and ethylene / propylene / diene monomer (EPDM) copolymers,
(4)スチレン/エチレン−ブテン/スチレンブロックコポリマー(SEBS)、スチレン/ブタジエン/スチレンブロックコポリマー(SBS)、スチレン/イソプレン/スチレンブロックコポリマー(SIS)またはスチレン/エチレン−プロピレン/スチレン(SEPS)ブロックコポリマー。
(5)エチレンと、アルキル(メタ)アクリレート(例えばメチルアクリレート)等の不飽和カルボン酸の塩またはエステルまたは酢酸ビニル等の飽和カルボン酸ビニルエステルの中から選択される少なくとも1種の化合物とのコポリマー。コモノマーの比率は40重量%以下にすることができる。
(4) Styrene / ethylene-butene / styrene block copolymer (SEBS), styrene / butadiene / styrene block copolymer (SBS), styrene / isoprene / styrene block copolymer (SIS) or styrene / ethylene-propylene / styrene (SEPS) block copolymer .
(5) Copolymer of ethylene and at least one compound selected from salts or esters of unsaturated carboxylic acids such as alkyl (meth) acrylates (for example, methyl acrylate) or saturated vinyl carboxylic acid esters such as vinyl acetate . The comonomer ratio can be up to 40% by weight.
不飽和モノマー(X)の残基が結合しているポリオレフィン幹ポリマーは不飽和モノマー(X)がグラフトしたポリエチレンまたは例えばラジカル重合で得られるエチレンとXのコポリマーにするのが好ましい。
不飽和モノマー(X)がグラフトするポリエチレンはエチレンのホモポリマーでもコポリマーでもよい。
The polyolefin backbone polymer to which the residue of the unsaturated monomer (X) is bonded is preferably a polyethylene grafted with the unsaturated monomer (X) or a copolymer of ethylene and X obtained, for example, by radical polymerization.
The polyethylene to which the unsaturated monomer (X) is grafted may be a homopolymer or a copolymer of ethylene.
コモノマーとしては以下が挙げられる:
1) α-オレフィン、好ましくは炭素数が3〜30のもの。例としては上記に挙げたものがある。このα-オレフィンを単独または2種以上の混合物の形で用いることができる。
2) 不飽和カルボン酸のエステル、例えばアルキル(メタ)アクリレート(アルキルは炭素数が24以下)、アルキルアクリレートまたはメタクリレートの例としては特にメタクリル酸メチル、アクリル酸エチル、アクリル酸n−ブチル、アクリル酸イソブチル、アクリル酸−2−エチルヘキシルが挙げられる、
3) 不飽和カルボン酸のビニルエステル、例えば酢酸ビニルまたはプロピオン酸ビニル、
4) ジエン、例えば、1,4−ヘキサジエン、
5) 上記コモノマーを複数有するポリエチレン。
Comonomers include the following:
1) α-olefin, preferably having 3 to 30 carbon atoms. Examples include those listed above. These α-olefins can be used alone or in the form of a mixture of two or more.
2) Esters of unsaturated carboxylic acids, such as alkyl (meth) acrylates (alkyl has up to 24 carbon atoms), examples of alkyl acrylates or methacrylates include methyl methacrylate, ethyl acrylate, n-butyl acrylate, acrylic acid Isobutyl, 2-ethylhexyl acrylate, and the like.
3) Vinyl esters of unsaturated carboxylic acids such as vinyl acetate or vinyl propionate,
4) Diene, such as 1,4-hexadiene,
5) Polyethylene having a plurality of the above comonomers.
複数のポリマーの混合物として混合されるポリエチレンは少なくとも50%(モル)、好ましくは75%のエチレンを含むのが好ましく、その密度は0.86〜0.98g/cm3にすることができる。MFI(190℃、2.16kgでのメルトフローインデックス)は20〜1000g/10分であるのが有利である。 The polyethylene mixed as a mixture of polymers preferably contains at least 50% (mole), preferably 75% ethylene, and its density can be 0.86 to 0.98 g / cm 3 . The MFI (melt flow index at 190 ° C., 2.16 kg) is advantageously 20 to 1000 g / 10 min.
ポリエチレンの例としては下記が挙げられる:
低密度ポリエチレン(LDPE)
高密度ポリエチレン(HDPE)
直鎖低密度ポリエチレン(LLDPE)
超低密度ポリエチレン(VLDPE)
メタロセン触媒で得られたポリエチレン、
EPRエラストマー(エチレン−プロピレンゴム)、
EPDMエラストマー(エチレン−プロピレン−ジエンモノマー)、
ポリエチレンとEPRまたはEPDMとの混合物、
エチレン/アルキル(メタ)アクリレートコポリマー((メタ)アクリレートの比率は60重量%以下、好ましくは2〜40重量%)
Examples of polyethylene include the following:
Low density polyethylene (LDPE)
High density polyethylene (HDPE)
Linear low density polyethylene (LLDPE)
Very low density polyethylene (VLDPE)
Polyethylene obtained with a metallocene catalyst,
EPR elastomer (ethylene-propylene rubber),
EPDM elastomer (ethylene-propylene-diene monomer),
A mixture of polyethylene and EPR or EPDM,
Ethylene / alkyl (meth) acrylate copolymer (the ratio of (meth) acrylate is 60% by weight or less, preferably 2 to 40% by weight)
グラフト化方法自体は当業者に公知である。
エチレン/不飽和モノマー(X)コポリマーの場合、すなわち、不飽和モノマー(X)がグラフトでない場合の不飽和モノマー(X)および必要に応じて用いられるその他のモノマーは、グラフトされるエチレンのコポリマーに関して説明した上記の中から選択することができる。
Grafting methods themselves are known to those skilled in the art.
In the case of an ethylene / unsaturated monomer (X) copolymer, ie unsaturated monomer (X) when the unsaturated monomer (X) is not grafted, and other monomers used as required, refer to the copolymer of ethylene to be grafted. You can choose from the descriptions above.
エチレン/無水マレイン酸コポリマーおよびエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマーを用いるのが有利である。このコポリマーは無水マレイン酸を0.2〜10重量%含み、アルキル(メタ)アクリレートを0〜40重量%、好ましくは5〜40重量%含むのが好ましい。このコポリマーのMFI(190℃、2.16kg)は5〜100である。アルキル(メタ)アクリレートは上記のものにすることができる。その融点は60〜120℃である。
不飽和モノマーXは、ポリオレフィン幹ポリマーに結合した鎖の1モル当たり平均して少なくとも2モル、好ましくは2〜5モルで存在するのが有利である。この不飽和モノマーXのモル数はFTIR分光分析法で簡単に求めることができる。
Preference is given to using ethylene / maleic anhydride copolymers and ethylene / alkyl (meth) acrylate / maleic anhydride copolymers. The copolymer preferably contains 0.2 to 10% by weight of maleic anhydride and 0 to 40% by weight, preferably 5 to 40% by weight of alkyl (meth) acrylate. The MFI (190 ° C., 2.16 kg) of this copolymer is 5-100. The alkyl (meth) acrylate can be as described above. Its melting point is 60-120 ° C.
The unsaturated monomer X is advantageously present in an average of at least 2 moles, preferably 2-5 moles, per mole of chain attached to the polyolefin backbone polymer. The number of moles of unsaturated monomer X can be easily determined by FTIR spectroscopy.
例えば、Xが無水マレイン酸で、ポリオレフィン幹ポリマーが重量平均分子量Mw=95,000g/molを有する場合は、無水物の量がXを含むポリオレフィン幹ポリマー全体の少なくとも1.5重量%、好ましくは2.5〜4重量%に相当することがわかっている。アミン末端を有するポリアミドの重量に関係があるこれらの値によって、ポリアミドブロックを有するグラフトコポリマー中のポリアミドおよび幹ポリマーの量が決まる。 For example, when X is maleic anhydride and the polyolefin backbone polymer has a weight average molecular weight M w = 95,000 g / mol, the amount of anhydride is at least 1.5% by weight of the total polyolefin backbone polymer containing X, preferably Is known to correspond to 2.5-4% by weight. These values, which are related to the weight of the polyamide having amine ends, determine the amount of polyamide and backbone polymer in the graft copolymer having polyamide blocks.
アミン末端を有するポリアミドにおける「ポリアミド」という用語は下記の縮合生成物を意味する:
(a) アミノカプロン酸、7−アミノヘプタン酸、11−アミノウンデカン酸および12−アミノドデカン酸のような1種または複数のアミノ酸またはカプロラクタム、エナントラクタムおよびラウリラクタム等の1種または複数のラクタム;
(b) ヘキサメチレンジアミン、ドデカメチレンジアミン、メタキシリレンジアミン、ビス(p−アミノシクロヘキシル)メタン、トリメチルヘキサメチレンジアミン等のジアミンと、イソフタル酸、テレフタル酸、アジピン酸、アゼライン酸、スベリン酸、セバシン酸およびドデカンジカルボキシル酸等のジアシッドとの1種または複数の塩または混合物;または
(c) コポリアミドを生成する複数のモノマーの混合物。
ポリアミドの混合物を用いることもできる。
The term “polyamide” in an amine-terminated polyamide means the following condensation product:
(a) one or more amino acids such as aminocaproic acid, 7-aminoheptanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid or one or more lactams such as caprolactam, enanthractam and laurylactam;
(b) Diamines such as hexamethylenediamine, dodecamethylenediamine, metaxylylenediamine, bis (p-aminocyclohexyl) methane, trimethylhexamethylenediamine, and isophthalic acid, terephthalic acid, adipic acid, azelaic acid, suberic acid, sebacin One or more salts or mixtures with acids and diacids such as dodecanedicarboxylic acid; or
(c) A mixture of monomers that forms a copolyamide.
Mixtures of polyamides can also be used.
コポリアミドはPA−6、PA−11、PA−12、6単位と11単位とのコポリアミド(PA−6/11)、6単位と12単位とのコポリアミド(PA−6/12)およびカプロラクタム、ヘキサメチレンジアミンおよびアジピン酸をベースとするコポリアミド(PA−6/6,6)を用いるのが有利である。これらのコポリアミドの利点はグラフト基の融点を選択できる点にある。 Copolyamides are PA-6, PA-11, PA-12, 6 units and 11 units copolyamide (PA-6 / 11), 6 units and 12 units copolyamide (PA-6 / 12) and caprolactam. It is advantageous to use a copolyamide based on hexamethylenediamine and adipic acid (PA-6 / 6,6). The advantage of these copolyamides is that the melting point of the graft group can be selected.
重合度は広範囲に変えることができ、重合度に応じてポリアミドまたはポリアミドオリゴマになる。本明細書では両者を区別しないで用いる。
モノアミン末端を有するポリアミドの場合、下記式の連鎖停止剤を使用すれば十分である:
The degree of polymerization can vary over a wide range, depending on the degree of polymerization, polyamide or polyamide oligomer. In the present specification, the two are used without distinction.
For polyamides with monoamine ends it is sufficient to use a chain terminator of the formula:
(ここで、R1は水素または20以下の炭素原子を含む直鎖または分岐鎖のアルキル基、R2は20以下の炭素原子を有する直鎖または分岐鎖のアルキルまたはアルケニル基、飽和または不飽和の脂環式基、芳香族基または上記の組み合わせを表す)
この連鎖停止剤は、例えばラウリルアミンまたはオレイルアミンにすることができる。
アミン末端を有するポリアミドの分子量は1000〜5000g/mol、好ましくは2000〜4000g/molにするのが好ましい。
Wherein R 1 is hydrogen or a linear or branched alkyl group containing up to 20 carbon atoms, R 2 is a linear or branched alkyl or alkenyl group containing up to 20 carbon atoms, saturated or unsaturated Represents an alicyclic group, an aromatic group or a combination of the above)
This chain terminator can be, for example, laurylamine or oleylamine.
The molecular weight of the polyamide having amine ends is preferably 1000 to 5000 g / mol, preferably 2000 to 4000 g / mol.
本発明のモノアミンオリゴマーを合成するのに好ましいアミノ酸またはラクタムモノマーはカプロラクタム、11−アミノ-ウンデカン酸またはドデカラクタムから選択される。好ましい一官能性連鎖停止剤はラウリルアミンとオレイルアミンである。
重縮合は一般に公知の通常の方法、例えば200〜300℃の温度で、真空下または不活性雰囲気下で、反応混合物を攪拌しながら行うことができる。オリゴマーの平均鎖長は重縮合するモノマーまたはラクタムと一官能性連鎖停止剤との初期モル比で決まる。平均鎖長の計算では一般に一つのオリゴマー鎖に対して一つの連鎖停止剤分子を計算する。
Preferred amino acid or lactam monomers for synthesizing the monoamine oligomers of the present invention are selected from caprolactam, 11-amino-undecanoic acid or dodecalactam. Preferred monofunctional chain terminators are laurylamine and oleylamine.
The polycondensation can be generally carried out in a known manner, for example, at a temperature of 200 to 300 ° C., under vacuum or in an inert atmosphere, while stirring the reaction mixture. The average chain length of the oligomer is determined by the initial molar ratio of the monomer or lactam to be polycondensed and the monofunctional chain terminator. In calculating the average chain length, one chain terminator molecule is generally calculated for one oligomer chain.
不飽和モノマー(X)を含むポリオレフィン幹ポリマーへのモノアミン基を有するポリアミドオリゴマーの付加は、オリゴマーのアミン官能基と不飽和モノマー(X)との反応で行うことができる。不飽和モノマー(X)は酸基または無水基を有するのが好ましく、従って、アミドまたはイミド結合を作る。
不飽和モノマー(X)を含むポリオレフィン幹ポリマーへのアミン末端を有するオリゴマーの付加は溶融状態で実行するのが好ましい。従って、オリゴマーと幹ポリマーとを一般に押出機で230〜280℃の温度で混合することができる。押出機中での溶融物の平均滞留時間は15秒〜5分の間、好ましくは1〜3分の間にする。この付加効率を上げるためには、遊離したポリアミドオリゴマー、すなわち最終ポリアミドブロックグラフトコポリマーを作るために未反応のものを選択的に抽出するのが好ましい。
The addition of the polyamide oligomer having a monoamine group to the polyolefin backbone polymer containing the unsaturated monomer (X) can be carried out by a reaction between the amine functional group of the oligomer and the unsaturated monomer (X). The unsaturated monomer (X) preferably has an acid group or an anhydride group and thus creates an amide or imide bond.
The addition of the oligomer having an amine terminus to the polyolefin backbone polymer containing the unsaturated monomer (X) is preferably carried out in the molten state. Therefore, the oligomer and the backbone polymer can generally be mixed at a temperature of 230 to 280 ° C. with an extruder. The average residence time of the melt in the extruder is between 15 seconds and 5 minutes, preferably between 1 and 3 minutes. In order to increase this addition efficiency, it is preferable to selectively extract free polyamide oligomers, ie, unreacted ones to make the final polyamide block graft copolymer.
不飽和モノマー(X)を含むポリオレフィン幹ポリマーの製造方法およびそのアミン末端を有するポリアミドへの付加は下記文献に記載されている。
本発明の熱可塑性組成物で用いるポリアミドブロックを有するグラフトコポリマーは厚さが10〜50ナノメーターのポリアミドの薄片(lamelles)を有するナノ構造組織で特徴付けられる。 The graft copolymer having polyamide blocks used in the thermoplastic composition of the present invention is characterized by a nanostructured structure having polyamide lamelles having a thickness of 10 to 50 nanometers.
このコポリマーは、少なくとも80℃、最高130℃で、極めて良好な耐クリープ性を有する。すなわち25kPa下では破断しない。
本発明で用いるコポリマーは押出機(単軸または二軸スクリュー押出機)、BUSSニーダー、ブラベンダーミキサー、一般には熱可塑性樹脂の混練で用いる通常の装置、好ましくは二軸スクリュー押出機を用いて溶融混合して製造できる。
This copolymer has very good creep resistance at least at 80 ° C. and up to 130 ° C. That is, it does not break under 25 kPa.
The copolymer used in the present invention is melted using an extruder (single screw or twin screw extruder), a BUSS kneader, a Brabender mixer, ordinarily equipment generally used for kneading thermoplastic resins, preferably a twin screw extruder. Can be manufactured by mixing.
本発明で用いる熱可塑性組成物は加工助剤、例えばシリカ、エチレンビスアミド、ステアリン酸カルシウムまたはステアリン酸マグネシウムを含むこともできる。上記組成物はさらに熱安定剤、酸化防止剤、紫外線安定剤、無機充填剤および着色顔料を含むこともできる。
本発明組成物は押出機中で一段階で調製できる。第1帯域にXを含む幹ポリマー(例えばエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマー)およびアミン末端を有するポリアミドを導入し、その後の複数の帯域で添加剤を導入する。全ての成分を押出機の第1帯域で導入することも可能である。
The thermoplastic composition used in the present invention may also contain processing aids such as silica, ethylene bisamide, calcium stearate or magnesium stearate. The composition may further contain a heat stabilizer, an antioxidant, an ultraviolet light stabilizer, an inorganic filler, and a color pigment.
The composition of the present invention can be prepared in one step in an extruder. A backbone polymer containing X in the first zone (eg, an ethylene / alkyl (meth) acrylate / maleic anhydride copolymer) and a polyamide with amine ends are introduced, followed by additives in multiple zones. It is also possible to introduce all components in the first zone of the extruder.
本発明の実施例
下記の成分(重量部)から共連続ナノ構造アロイの形の3つの熱可塑性組成物A、B、Cを製造した。成分の含有率は[表3]に示してある。
LOTADER4700(登録商標)はアルケマ社から入手できるエチレン/エチルアクリレート(29wt%)/無水マレイン酸(1.5wt%)ターポリマーで、MFIは7(ASTM D 1238規格に従って2.16kgの荷重下で190℃で測定、g/10分)。
LOTADER7500(登録商標)はアルケマ社から入手できるエチレン/エチルアクリレート(17.5wt%)/無水マレイン酸(2.9wt%)ターポリマーで、MFIは70。
LOTADER3210(登録商標)はアルケマ社から入手できるエチレン/ブチルアクリレート(6wt%)/無水マレイン酸(3wt%)ターポリマーで、MFIは5。
LOTADAR 4700® is an ethylene / ethyl acrylate (29 wt%) / maleic anhydride (1.5 wt%) terpolymer available from Arkema and has an MFI of 7 (190 under a load of 2.16 kg according to ASTM D 1238 standard). Measured at ° C., g / 10 min).
LOTADAR 7500® is an ethylene / ethyl acrylate (17.5 wt%) / maleic anhydride (2.9 wt%) terpolymer available from Arkema and has an MFI of 70.
LOTADAR 3210® is an ethylene / butyl acrylate (6 wt%) / maleic anhydride (3 wt%) terpolymer available from Arkema and has an MFI of 5.
モノ−NH2−末端を有するPA−6の分子量は2500g/molである。
IRGANOX 1098はCIBA社から入手可能な酸化防止剤である。
IRGAFOS 168はCIBA社から入手可能な安定剤である。
これらの成分を共回転二軸スクリュー押出機LEISTRITZ(登録商標)LSM 306−34に導入した(温度範囲=240〜280℃)。得られた生成物をペレット化後、袋詰めにした。
The molecular weight of PA-6 having a mono-NH 2 -terminus is 2500 g / mol.
IRGANOX 1098 is an antioxidant available from CIBA.
IRGAFOS 168 is a stabilizer available from CIBA.
These components were introduced into a co-rotating twin screw extruder LEISTTRIZ® LSM 306-34 (temperature range = 240-280 ° C.). The resulting product was pelletized and then packaged.
チューブ押出
組成物AおよびBを用いて種々の単層および二層チューブを押出し成形した。単層チューブの内径は6mm、外径は8mmである。二層チューブはアルケマ社から入手したリルサン(RILSAN、登録商標)(BESN BLACK P20 TL型)から成る内層と、上記組成物A、Bの外層(各層の厚さは1mmである)を共押出した(内径6mm、全外径10mm)。
Various single-layer and double-layer tubes were extruded using tube extrusion compositions A and B. The inner diameter of the single-layer tube is 6 mm, and the outer diameter is 8 mm. The double-layer tube was obtained by co-extrusion of an inner layer made of RILSAN (registered trademark) (BESN BLACK P20 TL type) obtained from Arkema and an outer layer of each of the compositions A and B (the thickness of each layer was 1 mm). (Inner diameter 6 mm, total outer diameter 10 mm).
耐加水分解性
単層チューブ(組成物A)をテキサコ(Texaco)社から入手した水/HAVOLINE XLC混合物(エチレングリコール+添加剤)(重量で50/50)中でエージングした。この水/HAVOLINE混合物中で130℃で1000時間エージングした後の機械的特性の変化を23℃で測定した。比較試験はポリプロピレン(PP)およびエチレン−プロピレン−ジエンモノマー(EPDM)コポリマーをベースにしたSANTOPRENE 8000 RUBBER 8201-90型の組成物(Advanced Elastomer Systems社から市販)を用いて行った。得られた結果は[表4]に示してある。
Hydrolysis resistant single layer tubes (Composition A) were aged in a water / HAVOLINE XLC mixture (ethylene glycol + additive) (50/50 by weight) obtained from Texaco. The change in mechanical properties after aging at 130 ° C. for 1000 hours in this water / HAVOLINE mixture was measured at 23 ° C. Comparative tests were performed using SANTOPRENE 8000 RUBBER 8201-90 type compositions (commercially available from Advanced Elastomer Systems) based on polypropylene (PP) and ethylene-propylene-diene monomer (EPDM) copolymers. The results obtained are shown in [Table 4].
耐熱エージング性
組成物Aを用いて製造した単層チューブと、PP+EPDM組成物を用いて製造した比較例の単層チューブとを、空気中で各種温度でエージングした。23℃で測定した機械的特性の変化は[表5]および[表6]に示してある。
A single-layer tube manufactured using the heat-resistant aging composition A and a single-layer tube of a comparative example manufactured using the PP + EPDM composition were aged in air at various temperatures. Changes in mechanical properties measured at 23 ° C. are shown in Table 5 and Table 6.
油中の耐エージング性
単層チューブ(本発明の組成物A、B、Cを用いて製造)をPSA/ルノーD47 1924規格に従ってエージング(時々接触)した。
各チューブおよびPP+EPDM(上記)をベースにした組成物を用いて製造したチューブをエルフトロフィー(Elf Trophy)DX15W40油に23℃で15秒間接触させた後、チューブを155℃の換気オーブン内に16時間入れた。明確な変化は観察できなかった。従って、チューブをVolkswagen TL 524 35規格(横方向引張)に従って評価した。
結果は[表7]に示してある。
After each tube and a tube made with a composition based on PP + EPDM (above) were contacted with Elf Trophy DX15W40 oil at 23 ° C. for 15 seconds, the tube was placed in a 155 ° C. ventilation oven for 16 hours. I put it in. A clear change could not be observed. Therefore, the tubes were evaluated according to the Volkswagen TL 524 35 standard (transverse tension).
The results are shown in [Table 7].
PP+EPDMをベースにした組成物とは違って、組成物A、B、Cの機械特性に対する熱エージングの影響はほとんど(または全く)ない。 Unlike compositions based on PP + EPDM, there is little (or no) influence of thermal aging on the mechanical properties of compositions A, B, C.
本発明のナノ構造熱可塑性組成物を熱的保護外層として有する二層構造
リルサン(RILSAN、登録商標)(BESN BLACK P20 TL型)(厚さ:1mm)から成る内層と本発明の組成物AおよびBの外層(厚さ:1mm)とを有する二層チューブを押出し成形した。チューブの内径は6mm、外径は10mmにした。
PSA D44 1959(ゴムおよびプラスチック−耐機械的摩擦性)規格およびSAE J2303(スリーブ絶縁の熱的効果)および規格に対応する特性に従ってチューブを評価した。
An inner layer composed of a bilayer Rilsan® (BESN BLACK P20 TL type) (thickness: 1 mm) having the nanostructured thermoplastic composition of the present invention as a thermal protective outer layer and the composition A of the present invention and A two-layer tube having an outer layer of B (thickness: 1 mm) was extruded. The inner diameter of the tube was 6 mm and the outer diameter was 10 mm.
The tubes were evaluated according to PSA D44 1959 (rubber and plastic-mechanical friction resistance) standard and SAE J2303 (thermal effect of sleeve insulation) and properties corresponding to the standard.
Claims (11)
上記組成物が、エチレン/無水マレイン酸およびエチレン/アルキル(メタ)アクリレート/無水マレイン酸コポリマーの中から選択されるポリオレフィン幹ポリマーと、少なくとも一種のポリアミドグラフト鎖とから成る、ポリアミドブロックを有するグラフトコポリマーを主成分とするナノ構造型の熱可塑性組成物であることを特徴とする使用。 For protecting at least one layer of a thermoplastic composition formed on a substrate at a temperature of 150 ° C. or higher when the coating layer is formed by coextrusion on the substrate to produce a pipe or tube. Use ,
The composition is composed of a polyolefin backbone polymer selected from among d styrene / maleic anhydride and ethylene / alkyl (meth) acrylate / maleic anhydride copolymer, and at least one polyamide graft chains, grafted with polyamide blocks Use characterized in that it is a nanostructured thermoplastic composition based on a copolymer.
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FR0501400 | 2005-02-11 | ||
FR0501400A FR2882060B1 (en) | 2005-02-11 | 2005-02-11 | USE OF THERMOPLASTIC COMPOSITIONS FOR THERMAL PROTECTION OF SUBSTRATES |
PCT/FR2006/000306 WO2006085007A1 (en) | 2005-02-11 | 2006-02-10 | Use of thermoplastic compositions for the thermal protection of substrates |
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EP1697448B1 (en) * | 2003-11-03 | 2012-12-26 | Porex Corporation | Sintered porous high melt-flow index materials and methods of making same |
US7399239B2 (en) * | 2006-12-04 | 2008-07-15 | Acushnet Company | Use of engineering thermoplastic vulcanizates for golf ball layers |
FR2912148B1 (en) * | 2007-02-07 | 2009-04-10 | Arkema France | POLYMERIC MATERIAL OF STYRENE / ANHYDRIDE TYPE, GRAFT HAVING IMPROVED PROPERTIES |
FR2918381B1 (en) * | 2007-07-02 | 2010-02-26 | Arkema France | USE OF GRAFT SMA COPOLYMERS IN LIQUID COMPOSITIONS |
FR2918380B1 (en) * | 2007-07-02 | 2009-09-04 | Arkema France | THERMOPLASTIC ELASTOMERIC MIXTURES AND COMPOSITIONS WITH IMPROVED PROPERTIES, PROCESS FOR PRODUCING THE COMPOSITIONS AND APPLICATIONS |
FR2918382B1 (en) * | 2007-07-02 | 2009-12-25 | Arkema France | MIXTURE OF GRAFT COPOLYMERS WITH POLYAMIDE BLOCKS AND ELASTOMERS FORMULATED WITH A RETICULATION SYSTEM, PROCESS FOR PRODUCING THE CORRESPONDING COMPOSITIONS AND USES THEREOF |
FR2925504B1 (en) | 2007-12-24 | 2010-03-05 | Arkema France | POLYMERIC ADDITIVES OBTAINED BY COPOLYMER SALIFICATION |
FR2930556B1 (en) * | 2008-04-28 | 2012-08-17 | Arkema France | COMPOSITION BASED ON POLYAMIDE GRAFT POLYMER AND USE THEREOF IN PHOTOVOLTAIC MODULES |
US20100176134A1 (en) * | 2008-07-22 | 2010-07-15 | Cramer Kenneth M | Retortable Closures and Containers |
US8628843B2 (en) * | 2008-10-24 | 2014-01-14 | Porex Corporation | Composite PTFE materials and applications thereof |
US8946352B2 (en) * | 2010-12-16 | 2015-02-03 | Empire Technology Development Llc | Melt processable poly (vinyl alcohol) blends and poly (vinyl alcohol) based membranes |
FR2969532B1 (en) * | 2010-12-23 | 2013-06-28 | Arkema France | ENCAPSULANT OF A PHOTOVOLTAIC MODULE |
FR2971625B1 (en) * | 2011-02-11 | 2013-02-15 | Arkema France | ENCAPSULATING A PHOTOVOLTAIC MODULE |
FR2971626B1 (en) * | 2011-02-11 | 2015-12-04 | Arkema France | BI-LAYER FILM OF A PHOTOVOLTAIC MODULE |
FR3003575B1 (en) | 2013-03-22 | 2015-03-27 | Arkema France | NANOSTRUCTURED THERMOPLASTIC COMPOSITION OF POLYOLEFIN TYPE GRAFFEE POLYAMIDE |
FR3006690B1 (en) | 2013-06-11 | 2015-05-29 | Arkema France | NANOSTRUCTURED THERMOPLASTIC COMPOSITION OF POLYOLEFIN TYPE GRAFFEE POLYAMIDE |
FR3016167B1 (en) | 2014-01-03 | 2017-05-19 | Arkema France | POLYPROPYLENE THERMOPLASTIC COMPOSITION AND POLYAMIDE GRAFTED POLYOLEFIN |
JP6535508B2 (en) * | 2015-05-08 | 2019-06-26 | ダイヤプラスフィルム株式会社 | Substrate film used for adhesive film for semiconductive process |
CA3154604C (en) | 2019-10-24 | 2024-01-30 | Chee Sern LIM | Polyamide compositions and articles made therefrom |
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JP2000313079A (en) * | 1999-03-16 | 2000-11-14 | Atofina | Polyamide-based multilayer tube for transporting gasoline |
JP2004510865A (en) * | 2000-10-06 | 2004-04-08 | アトフィナ | Mixture of polyamide block graft copolymer and flexible polyolefin |
JP2004299397A (en) * | 2003-03-21 | 2004-10-28 | Atofina | Multilayer structure composed of polyamide and graft copolymer containing polyamide block as base material |
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EP1449885B1 (en) * | 2003-02-18 | 2013-10-02 | Arkema France | Use of carbon nanotubes in compositions based on polyamides and polyolefins |
US7862872B2 (en) * | 2003-03-21 | 2011-01-04 | Arkema France | Multilayer structure based on polyamides and graft copolymers having polyamide blocks |
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JP2000313079A (en) * | 1999-03-16 | 2000-11-14 | Atofina | Polyamide-based multilayer tube for transporting gasoline |
JP2004510865A (en) * | 2000-10-06 | 2004-04-08 | アトフィナ | Mixture of polyamide block graft copolymer and flexible polyolefin |
JP2004299397A (en) * | 2003-03-21 | 2004-10-28 | Atofina | Multilayer structure composed of polyamide and graft copolymer containing polyamide block as base material |
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